Abstract
In this study, a novel water-insoluble zinc–Schiff base complex, Zn(II)-N-salicylaldehyde-2-hydroxyanil (abbreviated as Zn-salen), was synthesized and used as a heterogeneous photocatalyst for the activation of molecular oxygen to degrade organic pollutants in aqueous solution under visible light irradiation (λ ≥ 420 nm). The catalyst was characterized by FT-IR, UV–vis spectroscopy, NMR, and MS analysis. Zn-salen displays a selective adsorption and degradation of electropositive organics, such as rhodamine B (RhB), methylene blue (MB), and o-phenylenediamine (OPD). After using cetyl trimethyl ammonium bromide (CTAB) to change sulforhodamine B (SRB) into RhB-like electropositive molecule, the degradation of SRB increased up to 96 % after 4 h of irradiation, indicating that the selectivity arises from the charge interaction between the catalyst and substrates. Zeta potential of Zn-salen also reveals that the catalyst surface is negatively charged in neutral solution, suggesting that the catalyst is selective towards positively charged substrates due to an electrostatic force of attraction. The photocatalyst was active within a wide pH range (pH 3–11) and chemically stable and can be reused over 10 times. In addition, 1O2 and O2·− were involved in photocatalytic degradation but O2·− appears to be the primary reactive oxygen species.
Similar content being viewed by others
References
Ahmed, B., Limem, E., Abdel-Wahab, A., & Nasr, B. (2011). Photo-Fenton treatment of actual agro-industrial wastewaters. Ind Eng Chem Res., 50, 6673–6680.
Ali, M. M., & Sandhya, K. Y. (2016). Selective photodegradation and enhanced photo electrochemical properties of titanium dioxide–graphene composite with exposed (001) facets made by photochemical method. Sol Energ Mat Sol C., 144, 748–757.
Ardo, S., Achey, D., Morris, A. J., Abrahamsson, M., & Meyer, G. J. (2011). Non-Nernstian two-electron transfer photocatalysis at metalloporphyrin–TiO2 interfaces. J Am Chem Soc., 133, 16572–16580.
Boukha, Z., González-Prior, J., Rivas, B. D., González-Velasco, J. R., López-Fonseca, R., & Gutiérrez-Ortiz, J. I. (2016). Synthesis, characterization and behavior of Co/hydroxyapatite catalysts in the oxidation of 1,2-dichloroethane. Applied Catalysis B: Environmental, 190, 125–136.
Bozell, J. J., Hames, B. R., & Dimmel, D. R. (1995). Cobalt-Schiff base complex catalyzed oxidation of para-substituted phenolics. Preparation of benzoquinones. J. Org. Chem., 60, 2398–2404.
Buddhadeb, D., Sreyashi, J., Rajesh B., Pratap., Kumar, S., Subratanath K. (2007). Immobilization of copper Schiff base complexes in zeolite matrix: preparation, characterization and catalytic study. Applied Catalysis A: General, 318, 89–94
Chen, X., Ma, W. H., Li, J., Wang, Z. H., Chen, C. C., Ji, H. W., & Zhao, J. C. (2011a). Photocatalytic oxidation of organic pollutants catalyzed by an iron complex at biocompatible pH values: using O2 as main oxidant in a Fenton-like reaction. J Phys Chem C., 115, 4089–4095.
Chen, L. W., Ma, J., Li, X. C., Zhang, J., Fang, J. Y., Guan, Y. H., & Xie, P. C. (2011b). Strong enhancement on Fenton oxidation by addition of hydroxylamine to accelerate the ferric and ferrous iron cycles. Environ Sci Technol., 45, 3925–3930.
Chen, Y., Zhang, K., & Zuo, Y. (2013). Direct and indirect photodegradation of estriol in the presence of humic acid, nitrate and iron complexes in water solutions. Science of the Total Environment, 463–464, 802–809.
Claudio, P., Fabio, M., Riccardo, P., Domenico, M., Andrei, D., & Sergei, T. (2001). Synthesis and characterisation of tin(IV) and organotin(IV) derivatives 2-{[(2-hydroxyphenyl) imino] methyl} phenol. Inorg Chim Acta., 325, 103–114.
Cotanda, P., Lu, A., Patterson, J. P., Petzetakis, N., & O’Reilly, R. K. (2012). Functionalized organocatalytic nanoreactors: hydrophobic pockets for acylation reactions in water. Macromolecules, 45, 2377–2384.
Drozd, D., Szczubiałka, K., Łapok, Ł., Skiba, M., Patel, H., Gorun, S. M., & Nowakowska, M. (2012). Visible light induced photosensitized degradation of acid orange 7 in the suspension of bentonite intercalated with perfluoroalkyl perfluoro phthalocyanine zinc complex. Appl Catal B: Environ., 125, 35–40.
El-Medani, S. M., Ali, O. A. M., & Ramadan, R. M. (2005). Photochemical reactions of group 6 metal carbonyls with N-salicylidene-2-hydroxyaniline and bis-(salicylaldehyde) phenylenediimine. J Mol Struct., 738, 171–177.
Fang, Y. F., Huang, Y. P., Yang, J., Wang, P., & Cheng, G. W. (2011). Unique ability of BiOBr to decarboxylate D-Glu and D-MeAsp in the photocatalytic degradation of microcystin-LR in water. Environ Sci Technol., 45, 1593–1600.
Fatemeh, S. S., & Kamran, A. (2016). Linkers and coordinated solvent molecules; the two effective factors on formation of zinc oxide nanoparticles from metal–organic frameworks. Inorg Chem Commun., 63, 5–10.
Gonzalez-Olmos, R., Martin, M. J., Georgi, A., Kopinke, F. D., Oller, I., & Malato, S. (2012). Fe-zeolites as heterogeneous catalysts in solar Fenton-like reactions at neutral pH. Appl Catal B: Environ., 125, 51–58.
Gupta, K. C., Kumar, S. A., & Lin, C. C. (2009). Polymer-supported Schiff base complexes in oxidation reactions. Coord Chem Rev., 253, 1926–1946.
Hu, X. B., Xu, X., Ji, F. Y., & Fan, Z. H. (2009). Preparation and catalytic kinetic of hydrophobic photocatalytic catalysts. J Inorg Mater., 24, 1115–1120.
Huang, Y. P., Li, J., Ma, W. H., Cheng, M. M., Zhao, J. C., & Yu, J. C. (2004). Efficient H2O2 oxidation of organic pollutants catalyzed by supported iron sulfophenylporphyrin under visible light irradiation. J Phys Chem B., 108, 7263–7270.
Huang, Y. P., Ma, W. H., Li, J., Cheng, M. M., Zhao, J. C., Wan, L. J., & Yu, J. C. (2003). A novel β-CD-hemin complex photocatalyst for efficient degradation of organic pollutants at neutral pHs under visible irradiation. J Phys Chem B., 107, 9409–9414.
Kubacka, A., Fernández-García, M., & Colón, G. (2012). Advanced nanoarchitectures for solar photocatalytic applications. Chem Rev., 112, 1555–1614.
Liu, L., Jiang, D. L., McDonald, A., Hao, Y. Q., Millhauser, G. L., & Zhou, F. M. (2011). Copper redox cycling in the prion protein depends critically on binding mode. J Am Chem Soc., 133, 12229–12237.
Liu, S., Peng, J. J., Yang, H., Bai, Y., Li, J. Y., & Lai, G. Q. (2012). Highly efficient and convenient asymmetric hydrosilylation of ketones catalyzed with zinc Schiff base complexes. Tetrahedron Lett., 68, 1371–1375.
Mahamuni, N. N., & Adewuyi, Y. G. (2010). Advanced oxidation processes (AOPs) involving ultrasound for waste water treatment: a review with emphasis on cost estimation. Ultrason Sonochem., 17, 990–1003.
Marais, E., Klein, R., Antunes, E., & Nyokong, T. (2007). Photocatalysis of 4-nitrophenol using zinc phthalocyanine complexes. J Mol Catal A: Chem., 261, 36–42.
Meng, X., Qin, C., Wang, X. L., Su, Z. M., Li, B., & Yang, Q. H. (2011). Chiral salen-metal derivatives of polyoxometalates with asymmetric catalytic and photocatalytic activities. Dalton T., 40, 9964–9966.
Niu, P., Yang, Y., Yu, J. C., Liu, G., & Cheng, H. (2014). Switching the selectivity of the photoreduction reaction of carbon dioxide by controlling the band structure of a g-C3N4 photocatalyst. Chem. Commun, 50, 10837–10840.
O’Shea, K. E., & Dionysiou, D. D. (2012). Advanced oxidation processes for water treatment. J Phys Chem Lett., 3, 2112–2113.
Pinholt, C., Kapp, S. J., Bukrinsky, J. T., Hostrup, S., Frokjaer, S., Norde, W., & Jorgensen, L. (2013). Influence of acylation on the adsorption of GLP-2 to hydrophobic surfaces. Int J Pharm., 440, 63–71.
Qianqian, Z., Mami, I., Masahide, S., Takafumi, M., Ritsu, K., & Masami, F. (2016). Degradation and debromination of bromophenols using a free-base porphyrin and metalloporphyrins as photosensitizers under conditions of visible light irradiation in the absence and presence of humic substances. Appl Catal B: Environ., 183, 61–68.
Ryo, N., Shin-ichi, N., & Hiroaki, T. (2015). Visible light-driven selective aerobic oxidation of benzylalcohols to benzaldehydes by a Cu(acac)2−BiVO4-admicelle three-component heterosupramolecular photocatalyst. J Phys Chem C., 119, 11771–11776.
Sharma, R. K., Gulati, S., Pandey, A., & Adholeya, A. (2012). Novel, efficient and recyclable silica based organic–inorganic hybrid nickel catalyst for degradation of dye pollutants in a newly designed chemical reactor. Appl Catal B: Environ., 125, 247–258.
Silva, M., Calvete, M. J. F., Gonçalves, N. P. F., Burrows, H. D., Sarakha, M., Fernandes, A., Ribeiro, M. F., Azenha, M. E., & Pereira, M. M. (2012). Zinc(II) phthalocyanines immobilized in mesoporous silica Al-MCM-41 and their applications in photocatalytic degradation of pesticides. J Hazard Mater., 233, 79–88.
Sofianou, M. V., Psycharis, V., Boukos, N., Vaimakis, T., Yu, J., Dillertd, R., Bahnemann, D., & Christos, T. (2013). Tuning the photocatalytic selectivity of TiO2 anatase nanoplates by altering the exposed crystal facets content. Applied Catalysis B: Environmental, 142–143, 761–768.
Song, Q., Jia, M. K., Ma, W. H., Fang, Y. F., & Huang, Y. P. (2013). Heterogeneous degradation of toxic organic pollutants by hydrophobic copper-Schiff base complex under visible irradiation. Sci China Chem., 56, 1–8.
Song, Q., Ma, W. H., Jia, M. K., David, J., & Huang, Y. P. (2015). Degradation of organic pollutants in waters by a water-insoluble iron(III) Schiff base complex. Appl Catal A Gen., 505, 70–76.
Su, R., Sun, J., Sun, Y. P., Deng, K. J., Cha, D. M., & Wang, D. Y. (2009). Oxidative degradation of dye pollutants over a broad pH range using hydrogen peroxide catalyzed by FePz(dtnCl2)4. Chemosphere., 77, 1146–1151.
Tianyuan, X., Yun, L., Fei, G., Lin, L., & Yuting, O. (2013). Application of response surface methodology for optimization of azocarmine B removal by heterogeneous photo-Fenton process using hydroxy-iron–aluminum pillared bentonite. Appl Surf Sci., 280, 926–932.
Tseng, W. J., & Lin, R. D. (2014). BiFeO3/α-Fe2O3 core/shell composite particles for fast and selective removal of methyl orange dye in water. Journal of Colloid and Interface Science, 428, 95–100.
Vijayaraj, A., Prabu, R., Suresh, R., Sivaraj, C., Raaman, N., & Narayanan, V. (2011). New a cyclic Schiff-base copper(II) complexes and their electrochemical, catalytic, and antimicrobial studies. J Coord Chem., 64, 637–650.
Wang, X. L., Chen, N. L., Liu, G. C., Tian, A. X., Sha, X. T., & Ma, K. F. (2015). A series of CdII/ZnII coordination polymers containing helical chains constructed from a “V”-like bis-pyridyl-bis-amide and various dicarboxylates: assembly, structures, photoluminescent and selective photocatalysis. Inorg. Chim. Acta., 432, 128–135.
Wang, S. L., Fang, Y. F., Yang, Y., Liu, J. Z., Deng, A. P., Zhao, X. R., & Huang, Y. P. (2011). Catalysis of organic pollutant photodegradation by metal phthalocyanines immobilized on TiO2@SiO2. Chin Sci Bull., 56, 969–976.
Warren, J. E., Perkins, C. G., Jelfs, K. E., Boldrin, P., Chater, P. A., Miller, G. J., Manning, T. D., Briggs, M. E., Stylianou, K. C., Claridge, J. B., & Rosseinsky, M. J. (2014). Shape selectivity by guest-driven restructuring of a porous material. Angew. Chem. Int. Edn., 53, 4592–4596.
Wu, Q., Lin, S. W., Li, Y. G., & Wang, E. B. (2012). New supramolecular hybrids based on A-type Anderson polyoxometalates and Mn–Schiff-base complexes. Inorg Chim Acta., 382, 139–145.
Xiaopeng, W., Shouqiang, H., Nanwen, Z., Ziyang, L., & Haiping, Y. (2015). Facile synthesis of porous TiO2 photocatalysts using waste sludge as the template. Appl Surf Sci., 359, 917–922.
Ye, L., Yang, C., Tian, L., Zan, L., & Peng, T. (2011). Tunable photocatalytic selectivity of fluoropolymer PVDF modified TiO2. Appl Surf Sci., 257, 8072–8077.
Zhang, Z. H., Zhang, M. J., Deng, J., Deng, K. J., Zhang, B. G., Lv, K. L., Sun, J., & Chen, L. Q. (2013). Potocatalytic oxidative degradation of organic pollutant with molecular oxygen activated by a novel biomimetic catalyst ZnPz(dtn-COOH)4. Appl Catal B: Environ., 132, 90–97.
Zhao, X., Bu, X., Wu, T., Zheng, S., Wang, L., & Feng, P. (2013). Selective anion exchange with nanogated isoreticular positive metal-organic frameworks. Nature communications, 4, 2344.
Zhao, X. G., Huang, J. G., Wang, B., Bi, Q., Dong, L. L., & Liu, X. J. (2014). Preparation of titanium peroxide and its selective adsorption property on cationic dyes. Appl Surf Sci., 292, 576–582.
Zou, C., Zhang, Z. J., Xu, X., Gong, Q. H., Li, J., & Wu, C. D. (2012). A multifunctional organic–inorganic hybrid structure based on MnIII–porphyrin and polyoxometalate as a highly effective dye scavenger and heterogenous catalyst. J Am Chem Soc., 134, 87–90.
Zuo, Y., & Deng, Y. (1997). Iron (II) catalyzed photochemical decomposition of oxalic acid and generation of H2O2 in atmospheric liquid phases. Chemosphere, 35, 2051–2058.
Acknowledgments
This work was funded by the National Natural Science Foundation of China (Nos. 21407092, 21377067, and 21577077) and the Natural Science Foundation for Innovation Group of Hubei Province, China (No. 2015CFA021).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(PDF 65 kb)
Rights and permissions
About this article
Cite this article
Araya, T., Quan, S., Man-ke, J. et al. Selective Photocatalytic Degradation of Organic Pollutants Using a Water-Insoluble Zn–Schiff Base Complex. Water Air Soil Pollut 227, 284 (2016). https://doi.org/10.1007/s11270-016-2995-8
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11270-016-2995-8